Solid superacid catalysts comprising platinum metal

ABSTRACT

A sulfated solid catalyst is provided which comprises (1) oxide or hydroxide of Group III or Group IV element, e.g. zirconium, and (2) a first metal comprising a metal or combination of metals selected from the group consisting of platinum, palladium, nickel, platinum and rhenium, and platinum and tin. The catalyst may further comprise (3) a second metal selected from the group consisting of Group VIII elements, e.g. iron. One embodiment of the invention further comprises (4) a third metal selected from the group consisting of Group V, VI and VII elements, e.g. manganese. The catalyst of the invention is useful for the isomerization of normal alkanes having 4 to 40 carbon atoms per molecule, for the naphtha upgrading of a hydrocarbon feedstock and for the hydrocracking of a hydrocarbon feedstock.

BACKGROUND OF THE INVENTION

This invention relates to novel catalysts, methods of preparing the catalysts and a wide variety of catalytic processes employing the catalysts which are performed on hydrocarbons in the presence of hydrogen, including isomerization of hydrocarbons, particularly those with 4 to 10 carbon atoms per molecule and C₂₀ -C₄₀ waxy compounds. This invention also relates to novel catalytic hydrocracking and naphtha upgrading processes employing the catalysts of the invention.

BACKGROUND OF THE ART

Current commercial operations for n-butane isomerization include aluminum chloride and noble metal catalyzed processes. The aluminum chloride process, operated at relatively low temperature, is subject to corrosion and spent catalyst disposal problems. In addition, aluminum chloride processes require chloride injections to maintain acidity compensating for chloride lost to the environment. Furthermore, thermodynamic equilibrium limits the yield of isobutane. The process of the present invention causes less corrosion and has lesser environmental implications.

To obtain higher yields of isobutane, other isomerization processes have been developed. Liquid superacids containing a strong protic acid and a strong Lewis acid have been disclosed. See, U.S. Pat. Nos. 3,708,553; 3,766,286; 3,839,489; and 3,855,346.

Solid, very strongly acidic materials suitable for catalyzing hydrocarbon reactions have been prepared by others. For example, (1) Hino et al. disclose a butane isomerization catalyst prepared by treatment of zirconium oxides with sulfate ion, for example 1N sulfuric acid, and calcination of the product at 500° C. for three hours. Hino et al., "Reactions of Butane and Isobutane Catalyzed by Zirconium Oxide Treated With Sulfate Ion", J. Amer. Chem. Soc. (1979), 6439-41. Solid superacids suitable for catalyzing skeletal isomerizations of butane and isobutane have been prepared by exposing H₄ TiO₄ to 1N sulfuric acid and calcining in air at 500° C., as disclosed in (2) Hino et al., "Reactions of Butane and Isobutane Catalyzed by Titanium Oxide Treated With Sulphate Ion", J. S. C. Chem. Comm. (1979), 1148-9. (3) Hino et al., "Synthesis of Solid Superacid Catalyst with Acid Strength of H_(o) <-16.04", J. S. C. Chem. Comm. (1980), 851-2, disclose a preparation similar to that in reference (1) above, wherein Zr(OH)₄ obtained from different sources was calcined at temperatures up to 650° C. and found suitable for reactions of butane in a recirculation reactor at 25° C.

In (4) Japanese patent publication 87-344276/49, a solid superacid catalyst was prepared by impregnating a carrier comprising the hydroxide or oxide or a Group III or IV metal with a Group VIII metal¹ for use in producing lower paraffin hydrocarbons from shale oil.

In (5) Hosoi et al., Amer. Chem. Soc. Los Angeles Meeting, September 1988, Div. Petr. Chem. Pre. Print, 561-567, C₅ and C₆ hydrocarbons are isomerized at reaction temperatures of 140° to 200° C. using sulfated zirconia superacid catalyst with and without the addition of platinum, palladium, rhodium, nickel, ruthenium, iron, tungsten or molybdenum. Isomerization activity was found to be enhanced by addition of platinum.

In (6) Baba et al., Japanese Patent No. 61-2633932, Nov. 21, 1986, filed May 17, 1985, and (7) Baba et al., U.S. Pat. No. 5,036,035, hydrocarbons are isomerized at reaction temperatures below 400° C. using a catalyst obtained by impregnating Group VIII metals, e.g. nickel, platinum, ruthenium, rhodium, palladium, osmium or iridium, and sulfate ion or precursor thereof in a carrier made of Group IV metals, e.g. titanium, zirconium, hafnium, silicon, germanium or tin, and/or hydroxide or oxide of Group III metals, e.g. aluminum, gallium, indium and thallium, and stabilizing by roasting at 450°-800° C. for 5 to 16 hours. The catalysts disclosed maintained their activity over a period of 16 hours.

In (8) Ueda et al., Japanese Patent No. 62-246993, filed Apr. 2, 1986, paraffin hydrocarbons are thermally cracked at 150°-350° C. and over 50 atmospheres hydrogen pressure in the presence of a solid, highly acidic catalyst made by impregnating a Group VIII metal, e.g. nickel, platinum, ruthenium, rhodium, palladium, osmium or iridium, on a supporting body of a hydroxide or oxide of Group III or Group IV metals, e.g. titanium, zirconium, silicon, germanium, gallium or indium, followed by treating with sulfuric acid and roasting to stabilize the catalyst.

References (6), (7) and (8) indicate that addition of certain Group VIII metals improves the catalytic activities of the solid superacids and that these solid superacids are suitable for isomerization of alkanes and xylenes, and cracking of shale oil to light paraffins.

In (9) Hollstein et al., U.S. Pat. No. 4,918,041, disclose a sulfated, very strongly acidic catalyst which contains, in addition to oxide or hydroxide of Group III or Group IV element and Group VIII metal, as in references (6), (7) and (8) above, oxide or hydroxide of a Group V or Group VI or Group VII metal. This catalyst is, for example, useful in the isomerization of paraffin hydrocarbons.

In reference (9), as well as (10) Hollstein et al., U.S Pat. No. 4,956,519, and (11) Hsu et al., U.S. Pat. No. 5,019,671, it was also shown that sulfated metal oxide catalysts are active in isomerization reactions at low temperatures without the addition of chloride compounds which create corrosion problems and environmental problems.

Low temperature isomerization processes thermodynamically favor the creation of branched paraffins. This advantage of low temperature isomerization catalysts can be diminished or lost through increased deactivation of the catalyst, even at mild reaction conditions. Under such conditions, the solid superacid catalyst can be deactivated by trace amounts of impurities in the feed or by coke precursors formed in the reaction process thereby shortening the life of the catalyst. An advantage of the catalysts of the present invention, believed to result from use of two calcination steps, is that they have extremely long life.

Two possible approaches to minimize the deactivation of the catalyst include: (1) Operating the reaction under supercritical conditions (without hydrogen and hydrogenation-type metals) so that coke precursors are dissolved in the supercritical paraffin fluids; and (2) Using hydrogenation-type metals and hydrogen that can hydrogenate coke precursors and reduce the rate of deactivation. The present invention relates to the latter approach.

SUMMARY OF THE INVENTION

The present invention provides a sulfated, very strongly acidic catalyst comprising: (1) a support comprising Group III or Group IV oxide or hydroxide and (2) a first metal comprising a metal or mixture of metals selected from the group consisting of platinum; palladium; nickel; platinum and rhenium; and platinum and tin, and combinations thereof; wherein said sulfated support is calcined in a first calcination step before the introduction of said first metal, followed by a second calcination step.

The catalyst may further comprise Group VIII metals and/or Group V, VI or VII metals, or combinations thereof, incorporated on the support before the first calcination step. The use of at least two separate calcination steps has been found to produce superior catalysts for use in the processes of the present invention. In the presence of hydrogen, this catalyst is characterized by having high isomerization activity, naphtha upgrading activity, hydrocracking activity and extremely long catalyst life.

DETAILED DESCRIPTION OF THE INVENTION

The catalysts according to the present invention comprise a sulfated solid mixture of oxide or hydroxide of Group III or IV element and a first metal comprising a metal or mixture of metals selected from the group consisting of platinum; palladium; nickel; platinum and rhenium; and platinum and tin, and combinations thereof. The composition is calcined at least once prior to introduction of said first metal and again subsequent to said introduction. The use of separate calcination steps before and after incorporation of the first metal has been found to produce unexpectedly superior catalysts with regard to both extended catalyst life and conversion activity.

The catalyst may further comprise a second metal selected from the Group VIII metals and/or an additional, or "third", metal selected from the Group V, VI, and VII metals. A superior catalyst is thus obtained for use, for example, in the isomerization of paraffins and naphtha upgrading of hydrocarbon feeds. These catalysts have extremely long life, particularly in comparison to prior art catalysts. The support plus metal(s) can be calcined a single time prior to introduction of said first metal. Alternatively, the support can be calcined after the incorporation of each of said second and said third metals. Each of such calcination steps is performed under the conditions for the first calcination.

The catalysts of the present invention are prepared by the process of the present invention whereby the sulfated Group III or IV oxide or hydroxide, with or without the addition of said second and/or third metals, is calcined prior to the incorporation of said platinum, palladium, nickel, platinum/rhenium or platinum/tin. After incorporation of said first metal, the mixture is subjected to a second calcination. While it is contemplated that under some circumstances said second metal and said first metal may comprise the same element, they are distinct components of the catalyst by virtue of their incorporation either before or after the first calcination.

An essential element of the present invention is that the catalysts according to the invention are calcined at least twice. The first calcination is performed on the sulfated Group III or IV support with or without the addition of said second and third metals. That first calcination is carried out at a temperature in t he range from 450°-800° C. for a period of 1 to 30 hours, preferably 550°-750° C., more preferably around 725° C. for a period of time in the range from 1 to 2 hours. After the incorporation of said first metal, the second calcination is carried out at a temperature in the range of 400°-700° C. for a period of 1 to 30 hours, preferably 450°-550° C.. for a period of 10 hours. Preferably, the second calcination is carried out at a lower temperature than the first calcination. Combinations of temperature and time can be chosen in order to provide a desired degree of catalytic activity. For example, the catalyst prepared with a first calcination at 725° C. for 1 hour provides about the same initial conversion of n-butane to isobutane as one with a first calcination at 600° C. for 24 hours.

An advantage of the preparation process of the present invention is that it has been found to produce a more stable, long-lived catalyst. Catalyst life is particularly enhanced when the first calcination step is carried out at a higher temperature and for a shorter period of time than the second calcination step. Conducting the second calcination at temperatures above those specified above is believed to effect the stability of the catalyst by decreasing dispersion of said first metal on the support. Catalysts prepared according to the process of the present invention have been found to maintain activity for over 3000 hours. The process of the present invention is believed to maximize two of the functions of the catalyst; acidity and hydrogenation capacity.

The weight ratio of first metal to second metal is in the range 0.001:1 to 0.1:1, preferably 0.005:1 to 0.05:1. The weight ratio of third metal to second metal is in the range 0.1:1 to 2.0:1, preferably 0.2:1 to 1.0:1. The catalyst preferably contains a major amount of oxide or hydroxide of Group III or IV metal and a minor amount, preferably in the range of 0.02 to 15 weight percent, more preferably 1 to 8 weight percent, of total first metal, second metal and third metal.

The carrier or support for the catalyst according to the invention is an oxide or hydroxide of a Group III or IV element. Examples of suitable elements are titanium, zirconium, hafnium, aluminum, germanium, tin and lead. Preferred are zirconium, titanium, aluminum and silicon-aluminum and mixtures of two or more thereof. An essential component of the catalysts of the present invention is the first metal. Metals which can be used as said first metal according to the invention comprise platinum, palladium, and nickel and platinum/rhenium and platinum/tin mixtures and combinations thereof. A preferred embodiment of the catalyst comprises platinum.

The catalysts of the present invention are bifunctional catalysts; that is, they comprise metallic and acid sites which are believed to participate together in the mechanism pathways of the reforming reaction. The platinum, or other functionally equivalent metal, is believed mainly to serve as the catalytic site for hydrogenation and dehydrogenation reactions. The sulfated support is believed to provide the acid site for isomerization. Both sites are believed to participate in the hydrocracking and cyclization reactions.

One embodiment of the present invention comprises said second metal from Group VIII. Metals suitable as said second metal of the catalyst of the invention include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum and mixtures of two or more thereof. Of these, the most preferred is iron.

A further embodiment of the compositions of the present invention comprises addition of said third metal selected from Group V, Group VI and Group VII metals. Metals from Groups V, VI and VII which can be used as said third metal according to the invention comprise arsenic, antimony, bismuth, vanadium, niobium, tantalum, selenium, tellurium, chromium, molybdenum, tungsten, manganese and rhenium and mixtures of two or more thereof. Preferred among these is manganese.

The catalysts according to the invention may be prepared, for example, by sulfating a support of a Group III or IV metal oxide or hydroxide, calcining the mixture, impregnating said calcined mixture with an aqueous solution containing compounds of said first metal, and then subjecting said mixture to a second calcination. Embodiments of the catalyst of the present invention comprising additional classes of metals may be prepared by impregnating a sulfated support of a Group III or IV metal oxide or hydroxide with an aqueous solution containing compounds of said second metal, said third metal, or both said second and third metals, before the first calcination.

Alternatively, the support can be impregnated separately with solutions of the respective metal compounds. In this situation, the support plus metals can be calcined once or in separate calcination steps after the addition of each of said second metals and said third metals. In the latter process, the separate calcinations are performed under the conditions described for the first calcination step.

The catalysts according to the invention may also be prepared by co-precipitation of solid hydroxide of Group III or IV metals and the first metal and the respective second and/or third metals to be present in the catalyst, from aqueous solutions containing compounds of such metals. Again, the second and third metals present must be added before the first calcination step. The amount of the second and third metal hydroxide is typically in the range from 0.01 to 10.0 percent by weight of the total precipitated hydroxide. Mixtures of two or more Group V, Group VI and Group VII oxides or hydroxides may be employed.

The first metal is added thereafter and the mixture is then calcined again. In such method, the amount of the first metal is typically in the range from 0.01 to 50 percent by weight of the total precipitated hydroxide and varies for each metal. For platinum as first metal, the preferred range is 0.2 to 10 weight percent; for palladium, less than 1 weight percent; and for nickel, in the range of 1 to 10 weight percent.

Solutions of metal compounds which can be used in the preparation of catalysts according to the invention, by impregnation or co-precipitation, are known in the art. For example for the second and third metals, nitrates of iron and of manganese can be used, for example, to incorporate those metals in the catalyst. Solutions of zirconium oxychloride or of zirconyl nitrate can be used, for example, to prepare a zirconium support for the catalyst according to the invention. Various other solutions can be employed as needed.

Solution of said first metals which can be used in the preparation of catalysts of the present invention are also known in the art. For example, chloroplatinic acid, tetra-amine-platinum complex, platinum chlorides and platinum acetylacetonate can be used to incorporate platinum in the catalyst. Nickel nitrate, nickel acetate, nickel acetylacetonate and nickel chlorides can be used to incorporate nickel in the catalyst. Palladium acetate, palladium acetylacetonate and palladium chlorides can be used to incorporate palladium in the catalyst. Rhenium nitrate, rhenium oxychloride and rhenium chlorides can be used to incorporate rhenium in the catalyst. Various other solution of platinum or the other first metals can used as needed. This impregnation can be conducted in either aqueous or organic phase.

Sulfate ion may be supplied to the catalyst according to the invention by treatment of the solid catalyst with sulfuric acid, for example, 0.01-10N sulfuric acid, preferably 0.1-5N sulfuric acid. Other compounds, such as ammonium sulfate, capable of providing sulfate ion can be employed. Compounds such as hydrogen sulfide or sulfur dioxide or mercaptans, capable of forming sulfate ions upon calcining, can also be used. Preferred catalysts for use according to the invention are those which have been sulfated with ammonium sulfate.

The catalysts according to the invention contain substantial amounts of sulfate ion, preferably amounts in the range of 0.5 to 20 weight percent based on total catalyst, preferably 2 to 8 weight percent.

Preferred catalysts according to the present invention include the following compositions: platinum/iron/SO₄ =/ZrO₂ ; platinum/rhenium/iron/SO₄ =/ZrO₂ ; platinum/rhenium/iron/manganese/SO₄ =/ZrO₂ ; platinum/rhenium/SO₄ =/ZrO₂ ; nickel/iron/SO₄ =/ZrO₂ ; nickel/iron/manganese/SO₄ =/ZrO₂ ; nickel/manganese/SO₄ =/ZrO₂ ; platinum/tin/iron/SO₄ =/ZrO₂ ; platinum/tin/iron/manganese/SO₄ =/ZrO₂

The catalysts according to the invention may be used in a variety of hydrocarbon conversion processes, including isomerization of normal alkanes and the naphtha upgrading and hydrocracking of hydrocarbon feeds. In these processes, feed is contacted with catalyst in the presence of hydrogen. The catalysts of the present invention have been found to have an extremely long catalyst life, maintaining activity over a period of more than 3000 hours.

In one embodiment of the invention, the catalysts are used to isomerize alkanes having four to twenty, and preferably four to ten, carbon atoms, namely, butane, pentane, hexane, heptane, octane, nonane and decane, to convert the straight chain hydrocarbons into branched chain hydrocarbons having higher octane number for use as motor fuel or, as in the case of butane, having enhanced value as an intermediate for such products as tertiary butyl alcohol and high octane alkylates. In another application, the catalysts are used in the isomerization of C₂₀ to C₄₀ waxy compounds to produce lubricating oil compounds.

We have found that adding of platinum, palladium, nickel, platinum/rhenium or platinum/tin to the compositions disclosed in Hollstein et al., U.S. Pat. No. 4,918,041, and Baba et al., U.S. Pat. No. 5,036,035, and subjecting the mixture to a second calcination step produces a surprisingly superior catalyst for the isomerization of alkanes. These catalysts have an unexpectedly longer catalyst life than those of the prior art.

These solid superacid catalysts containing platinum, palladium, nickel, platinum/rhenium or platinum/tin can selectively isomerize C₄ to C₁₀ alkanes to yield highly branched alkanes without producing much C₁ to C₃ light ends. The prior art gives no indication of the superior results which may be obtained by a separate calcination step after the addition of these metals to the solid superacid catalysts comprising Group VIII metal or Group VIII metal plus Group V, VI or VII metal on a sulfated Group III or IV element support. Advantages of the catalysts according to the present invention include that they have longer life, cause less corrosion to the reaction system, produce less environmental problems than prior art catalysts and are regenerable.

The isomerization is carried out by contacting the hydrocarbon feed with the solid catalyst at temperatures in the range of 0° to 400° C., preferably in the range of 20° to 250° C., and at a pressure in the range of 15 to 1100 psig, preferably in the range of 400 to 800 psig. The isomerization is conducted in the presence of hydrogen. The mole ratio of hydrogen to hydrocarbon is preferably in the range of 0.1:1 to 10:1. Inert gas, such as nitrogen, helium or argon may be employed together with H₂. Generally, a temperature is used which is sufficiently high to obtain a desired rate of reaction, but not so high as to result in undesired cracking of the feed.

A preferred isomerization process comprises a pre-reduction phase and a start-up phase. The pre-reduction phase involves subjecting dry catalyst loaded into the reactor vessel to heat for a certain period of time. According to one embodiment of the process of the invention, the catalyst is dried overnight in air at a temperature in the range from 350° C. to 500° C. Subsequently, the temperature is adjusted to the pre-reduction temperature and the air is replaced with nitrogen. The pre-reduction phase is carried out in a hydrogen atmosphere. This phase is preferably conducted at pressures between atmospheric pressure and the ultimate reaction pressure.

For platinum-containing embodiments of the catalyst, the pre-reduction phase involves heating the catalyst under hydrogen to a temperature in the range from 50° to 300° C., preferably 100° to 200° C., more preferably 125° to 175° C. For nickel-containing catalysts, the pre-reduction temperature may be as high as 400° to 500° C. The duration of the pre-reduction phase is dependent on the H₂ flow and the amount of platinum or other first metal to be reduced. This, in turn, is a function of the size of the reactor. For example, at a flow rate of 100 cc H₂ per minute for a 5 cc sample of catalyst comprising 0.34% platinum, 20 minutes would be a suitable duration for the pre-reduction phase.

According to one embodiment of the process of the invention, following the pre-reduction treatment, the following reactor start-up phase conditions should be employed. The temperature of the reactor vessel is reduced to a range between room temperature and the pre-reduction temperature, the pressure is increased and the hydrocarbon feed is introduced at LHSV of 1 to 5 hr⁻¹. The temperature is then gradually increased at a rate of approximately 1° to 3° C. per minute until the desired isomerization reaction temperature is reached.

The catalysts according to the invention are, in another embodiment of the invention, used in naphtha upgrading of a hydrocarbon feed to produce more highly branched hydrocarbons with higher octane number. Hydrocarbon feed suitable for naphtha upgrading in the process of the present invention include whole reforming feed and fractions thereof. A preferred naphtha upgrading process comprises a pre-reduction phase and a start-up phase. The pre-reduction and start-up procedures are as described above in connection with the isomerization process.

The naphtha upgrading process is carried out by contacting the hydrocarbon feed with the solid catalyst at temperatures in the range of 0° to 400° C., preferably in the range of 20° to 250° C., and at a pressure in the range of 15 to 1100 psig, preferably in the range of 400 to 800 psig. The process of the invention is conducted in the presence of hydrogen. The mole ratio of hydrogen to hydrocarbon is preferably in the range of 0.1:1 to 10:1. Inert gas, such as nitrogen, helium or argon may be employed together with H₂.

The catalysts according to the invention are, in another embodiment, used in hydrocracking of a hydrocarbon feed to produce lighter, branched hydrocarbons with higher octane number than the components of the feedstock. Hydrocarbon feed suitable for hydrocracking in the process of the present invention include any conventional hydrocracking feed, including naphtha feed. A preferred hydrocracking process comprises a pre-reduction phase and a start-up phase. The pre-reduction and start-up procedures are as described above in connection with the isomerization process.

The hydrocracking process is carried out by contacting the hydrocarbon feed with the solid catalyst at temperatures in the range of 0° to 400° C., preferably in the range of 20° to 250° C., and at a pressure in the range of 15 to 1100 psig, preferably in the range of 400 to 800 psig. The process of the invention is conducted in the presence of hydrogen. The mole ratio of hydrogen to hydrocarbon is preferably in the range of 0.1:1 to 10:1. Inert gas, such as nitrogen, helium or argon may be employed together with H₂.

EXAMPLE 1

A sulfated zirconia based catalyst containing iron (Group VIII) and manganese (Group VII) was prepared by co-precipitation according to Hollstein et al., U.S. Pat. No. 4,918,041, which is incorporated herein by reference.

Zirconyl nitrate (462.46 g), ferric nitrate (26.74 g) and manganese nitrate (5.62 g) were dissolved in de-ionized water to make 1 liter of Solution A. 260 g of concentrated ammonium hydroxide were diluted with sufficient de-ionized water to make 1 liter of Solution B. 500 ml of de-ionized water were added to a 5 liter Morton flask. Solution A and Solution B were added concurrently through two addition funnels to the Morton flask slowly with rapid stirring. The temperature for the precipitation reaction was maintained at approximately 65° C. The pH of the resulting reaction mixture was maintained at approximately 7.0. The reaction slurry was filtered and the filter cake was washed with de-ionized water several times until the filtrate was nitrate free. The damp cake was applied to perforated plates, placed in a tray and dried overnight at 150° C.

The dried pellets were added slowly to a beaker containing 1.0N sulfuric acid solution at room temperature. The amount of sulfuric acid was determined by the following ratio of 15 ml of 1.0N sulfuric acid per gram of pellet. The sulfuric acid solution was decanted after the pellets had been soaked for 2 hours. The pellets were then calcined at 725° C. for 1 hour. The iron and manganese concentration in the final catalyst were 1.5% and 0.5%, respectively (Preparation I).

The pellets from Preparation I (20-40 mesh) were subsequently impregnated with an aqueous solution (incipient wetness) of chloroplatinic acid. The preparation was dried overnight at 120° C. and then calcined at 450° C. for 16 hours. The final catalyst had 0.5 weight percent platinum.

EXAMPLE 2

Sulfated zirconia based catalyst containing iron and manganese was prepared by the co-precipitation method similar to that of Example 1, except that ammonium sulfate, rather than sulfuric acid, was used to sulfate the catalyst. The sulfation was carried out prior to calcining of the catalyst. The dried pellets from the overnight drying step were treated with ammonium sulfate to incorporate 4-8% of sulfate ion in the catalyst, using incipient wetness technique, and then calcined at 725° C. for 1 hour (Preparation II).

25 g of pellets from Preparation II (20-40 mesh) were impregnated with a water solution containing nickel nitrate. This preparation was dried overnight and calcined for 16 hours between 450°-550° C. The amount of nickel in the final catalyst was 5%.

EXAMPLE 3

25 g of pellets from Preparation II (20-40 mesh) were impregnated with a water solution containing palladium chloride. This preparation was dried overnight and calcined between 450°-550° C. for 16 hours. The amount of palladium in the final catalyst was 0.5%.

EXAMPLE 4

A Pt/Fe/Mn/SO₄ =/ZrO₂ catalyst containing 0.25 wt % platinum was prepared according to the procedure of Example 1 above for use in the isomerization of a mixture of n-hexane (87%) and n-pentane (13%). Before starting the reaction, the catalyst was dried overnight at 450° C. in flowing air. Subsequently, the reactor was cooled to 150° C. and nitrogen was passed over the catalyst. This was followed by 2 hours of hydrogen flow over the catalyst and reduction of the temperature to room temperature. The reaction conditions and product distribution are presented in Table I.

EXAMPLE 5

A Pt/Fe/Mn/SO₄ =/ZrO₂ catalyst containing 0.34 wt % platinum was prepared according to the procedure of Example 1 and pretreated as described in Example 6 above for use in the hydrocracking and isomerization of cyclohexane. The reaction conditions and product distribution are presented in Table II.

                  TABLE I                                                          ______________________________________                                         Isomerization of n-Hexane (87%) and n-Pentane (13%)                            Catalyzed by Pt/Fe/Me/SO.sub.4.sup.= /ZrO.sub.2 with 0.25 wt %                 ______________________________________                                         Pt                                                                             Temp C.          200     200                                                   Press. PSIG      500     500                                                   LHSV, 1/hr       2       4                                                     H2, cc/min       100     100                                                   ave. of (hrs)    50-90   95-111                                                ______________________________________                                         wt %                                                                           ______________________________________                                         C1               0.24    0.08                                                  C2               0.68    0.17                                                  C3               2.74    0.84                                                  I-C4             5.96    3.19                                                  N-C4             1.8     0.59                                                  I-C5             3.37    1.89                                                  N-C5             1.09    0.54                                                  2,2DMC4          21.23   16.29                                                 2,3DMC4          7.97    8.44                                                  2MC5             26.19   28.54                                                 3MC5             15.99   17.92                                                 N-C6             11.54   13.84                                                 2,2DMC5          0       0.03                                                  2,4DMC5          0.55    2.38                                                  2,2,3TMC4        0       0.01                                                  3,3DMC5          0       0.02                                                  2MC6             0.06    0.12                                                  2,3DMC5          0       0.04                                                  3MC6             0.05    0.17                                                  2,2,4-TMC5       0.01    0.1                                                   N-C7             0       0.06                                                  ______________________________________                                    

                  TABLE II                                                         ______________________________________                                         Hydrocracking and Isomerization of Cyclohexane                                 Catalysed by Pt/Fe/Mn/SO.sub.4.sup.= /ZrO.sub.2 with 0.34 wt %                 ______________________________________                                         Pt                                                                             Temp. C.   181         200      220                                            Pres. PSIG 500         500      500                                            LHSV, (1/hr)                                                                              2           2        2                                              H2, cc/min 100         100      100                                            Ave. hr of 75-118      120-157  185-213                                        ______________________________________                                         wt %                                                                           ______________________________________                                         Total C1-C3                                                                               0.24        0.87     1.77                                           Total C4   5.58        13.87    20.14                                          Total C5   2.22        7.01     11.6                                           2,2DMC4    1.06        1.99     2.2                                            2,3DMC4    1.18        1.89     5                                              2MC5       4.19        4.33     7.61                                           3MC5       2.55        3.92     4.61                                           n-C6       2.1         2.94     3.62                                           MCYC5      47.09       37.92    26.92                                          CYC6       30.86       19.77    12.05                                          Total C6+  3.04        6.76     13.71                                          ______________________________________                                    

EXAMPLE 6

A Pt/Fe/Mn/SO₄ =/ZrO₂ catalyst containing 0.34 wt % platinum was prepared according to the procedure of Example 1 and pre-treated as described in Example 6 above for use in the upgrading of naphtha using IBP190 feed. Table III presents the reaction conditions and product distribution.

EXAMPLE 7

A Pt/Fe/Mn/SO₄ =/ZrO₂ catalyst containing 0.34 wt % platinum was prepared according to the procedure of Example 1 and pre-treated as described in Example 6 above for use in the hydrocracking and upgrading of naphtha using whole reforming feed. The reaction conditions and product distribution are presented in Table IVA and Table IVB.

EXAMPLE 8

A Ni/Fe/Mn/SO₄ =/ZrO₂ catalyst containing 7.5 wt % nickel was prepared according to the procedure of Example 2 and pre-treated as described in Example 6 above for use in the upgrading of naphtha using IBP190 feed in the presence of hydrogen. The reaction conditions and product distribution are presented in Table V.

                  TABLE III                                                        ______________________________________                                         Naphtha Upgrading of IBP190 Feed                                               Catalyzed by Pt/Fe/Mn/SO.sub.4.sup.= /ZrO.sub.2 with 0.34 wt %                 ______________________________________                                         Pt                                                                             Temp, C.               207      220                                            Pres. PSIG             500      500                                            LHSV, (1/hr)           2        2                                              H2, ml/min             100      100                                            Ave. of (hr)           100-300  1800-2000                                      ______________________________________                                         wt %       IBP 190                                                             ______________________________________                                         Total C1-C3                                                                               0           5.46     3.9                                            i-C4       0           11.2     9.7                                            Total C4   0           12.1     10.3                                           i-C5       0.3         4.91     3.9                                            Total C5   1.9         6.7      5.4                                            2,2DMC4    0.66        10.4     7.8                                            2,3DMC4    1.94        7.5      7.8                                            2MC5       15.5        21       21.9                                           3MC5       9.6         13.1     13.2                                           n-C6       27.4        10.3     10.2                                           MCYC5      14.34       5.8      8.8                                            Bezene     2.5         0        0                                              CYC6       8.93        3.10     4.8                                            Total C6+  14.37       4.62     5.9                                            ______________________________________                                    

                  TABLE IVA                                                        ______________________________________                                         Hydrocracking and Naphtha Upgrading of Whole Reforming Feed                    Catalyzed by Pt/Fe/Mn/SO.sub.4.sup.= /ZrO.sub.2 with 0.34 wt %                 ______________________________________                                         Pt                                                                             Temp. C.                200                                                    Pres. PSIG              500                                                    LHSV, (1/hr)            2                                                      H2, (cc/min)            100                                                    ______________________________________                                         wt %         Whole Feed Product (200 hr)                                       ______________________________________                                         Paraffins    25         11                                                     i-Paraffins  28         53                                                     Aromatics    12         0                                                      Naphthenes   31         36                                                     Olefins      1          0                                                      Benzene      0.5        0                                                      T90 (F)      345        254                                                    ______________________________________                                    

                  TABLE IVB                                                        ______________________________________                                         Hydrocracking and Naphtha Upgrading of Whole Reforming Feed                    Catalyzed by Pt/Fe/Mn/SO.sub.4.sup.= /ZrO.sub.2 with 0.34 wt % Pt              Number of carbon Whole feed                                                                               Product                                             ______________________________________                                         C3               0         2.46                                                C4               0         21.27                                               C5               0.81      12.03                                               C6               18.47     25.3                                                C7               22.33     20.59                                               C8               19.95     11.52                                               C9               17.35     6.61                                                C10              14.1      0.1                                                 C11              3.3       0                                                   ______________________________________                                    

                  TABLE V                                                          ______________________________________                                         Naphtha Upgrading of IBP190 Feed                                               Catalyzed by Ni/Fe/Mn/SO.sub.4.sup.= /ZrO.sub.2 with 7.5 wt %                  ______________________________________                                         Ni                                                                             Temp, C.                  215                                                  Pres. PSIG                500                                                  LHSV, (1/hr)              2                                                    H2, ml/min                100                                                  Aver. of (hr)             75-90                                                ______________________________________                                         wt %             IBP 190                                                       ______________________________________                                         Total C1-C3      0        3.9                                                  i-C4             0        12.9                                                 Total C4         0        13.7                                                 i-C5             0.3      4.6                                                  Total C5         1.9      6.2                                                  2,2DMC4          0.6      4.7                                                  2,3DMC4          1.9      7.2                                                  2MC5             15.5     19.1                                                 3MC5             9.6      11.9                                                 n-C6             27.4     9.9                                                  MCYC5            14.3     9.1                                                  Benzene          2.5      0                                                    CYC6             8.9      3.9                                                  Total C6+        14.4     10.6                                                 ______________________________________                                    

EXAMPLE 9

A Pd/Fe/Mn/SO₄ =/ZrO₂ catalyst containing 0.5 wt % palladium was prepared according to the procedure of Example 3 and pre-treated according to Example 6 for use in the upgrading of naphtha using IBP190 feed. The reaction conditions and product distribution are presented in Table VI.

                  TABLE VI                                                         ______________________________________                                         Naphtha Upgrading of IBP 190 Feed                                              Catalyzed by Pd/Fe/Mn/SO.sub.4.sup.= /ZrO.sub.2 with 0.5 wt %                  ______________________________________                                         Pd                                                                             Temp, C.                  215                                                  Pres. PSIG                500                                                  LHSV, (1/hr)              2                                                    H2, ml/min                100                                                  Aver. of (hr)             65-90                                                ______________________________________                                         wt %             IBP 190                                                       ______________________________________                                         Total C1-C3      0        5.2                                                  i-C4             0        6.1                                                  Total C4         0        6.7                                                  i-C5             0.3      2.5                                                  Total C5         1.9      3.5                                                  2,2DMC4          0.6      10.3                                                 2,3DMC4          1.9      7.4                                                  2MC5             15.5     24.9                                                 3MC5             9.6      17                                                   n-C6             27.4     14.9                                                 MCYC5            14.3     4.1                                                  Benzene          2.5      0                                                    CYC6             8.9      1.9                                                  Total C6+        14.4     3.9                                                  ______________________________________                                     

The invention claimed is:
 1. A catalyst composition comprising a mixture of:(a) a sulfated support comprising oxide or hydroxide of Group III or Group IV elements; and (b) a first metal comprising a metal or mixture of metals selected from the group consisting of platinum; palladium; nickel; platinum and rhenium; and platinum and tin, and combinations thereof;wherein said catalyst is prepared by the steps comprising: (1) calcining said sulfated support in a first calcination step; (2) introducing said first metal into said sulfated support; and (3) calcining said sulfated support and said first metal in a second calcination step;wherein the conditions of said second calcination step comprise a lower temperature than said first calcination step.
 2. A catalyst composition prepared by:(a) sulfating a support comprising oxide or hydroxide of Group III or Group IV elements; (b) calcining said support in a first calcination step; (c) introducing a first metal comprising a metal or mixture of metals selected from the group consisting of platinum; palladium; nickel; platinum and rhenium; and platinum and tin on said support, and combinations thereof, and (d) calcining said support and said first metal in a second calcination step;wherein the conditions of said second calcination step comprise a lower temperature than said first calcination step.
 3. The composition of claim 1 or 2 wherein the conditions of said first calcination step comprise a temperature in the range of 450° to 800° C. and a duration of 1 to 30 hours.
 4. The composition of claim 3 wherein said temperature is in the range of 550° to 750° C.
 5. The composition of claim 1 or 2 wherein the conditions of said second calcination step comprise a temperature in the range of 400° to 700° C. and a duration of 1 to 30 hours.
 6. The composition of claim 5 wherein said temperature is in the range of 450° to 550° C.
 7. The composition of claim 1 or 2 wherein said support comprises oxide or hydroxide of zirconium, titanium, aluminum or mixtures thereof.
 8. The composition of claim 7 wherein said support comprises oxide or hydroxide of zirconium.
 9. The composition of claim 1 or 2 wherein said first metal is platinum.
 10. The composition of claim 1 or 2 further comprising at least one second metal selected from the group consisting of Group VIII elements, wherein said catalyst is prepared by adding said second metal to said sulfated support before said first calcination step.
 11. The composition of claim 10 wherein said second metal is iron.
 12. The composition of claim 1 or 2 further comprising at least one additional metal selected from the group consisting of Group V, Group VI and Group VII elements, wherein said catalyst is prepared by adding said additional metal to said sulfated support before said first calcination step.
 13. The composition of claim 12 wherein said third metal is manganese.
 14. A catalyst composition comprising a mixture of:(a) a sulfated support comprising oxide or hydroxide of Group III or Group IV elements; (b) a first metal comprising a metal or mixture of metals selected from the group consisting of platinum; palladium; nickel; platinum and rhenium; and platinum and tin, and combinations thereof; (c) at least one second metal selected from group consisting of Group VIII elements; and (d) at least one third metal selected from the group consisting of Group V, Group VI and Group VII elements;wherein said catalyst is prepared by the steps comprising: (1) calcining said mixture of sulfated support, second metal and third metal in a first calcination step; (2) introducing said first metal into said mixture; and (3) calcining said mixture and said first metal in a second calcination step;wherein the conditions of said second calcination step comprise a lower temperature than said first calcination step.
 15. The composition prepared by:(a) forming a mixture by the steps of (i) sulfating a support comprising oxide or hydroxide of Group III or Group IV elements; (ii) introducing on said support at least one second metal selected from group consisting of Group VIII elements; and (iii) introducing on said support at least one third metal selected from the group consisting of Group V, Group VI and Group VII elements; (b) calcining the mixture comprising said support, said second metal and said third metal in a first calcination step; (c) introducing on said mixture a first metal comprising a metal or mixture of metals selected from the group consisting of platinum; palladium; nickel; platinum and rhenium; and platinum and tin, and combinations thereof; and (d) calcining said mixture and said first metal in a second calcination step;wherein the conditions of said second calcination step comprise a lower temperature than said first calcination step.
 16. The composition of claim 14 or 15 wherein said first calcination step comprises separately calcining said sulfated support, said second metal and said third metal subsequent to the introduction of each of said second metal or metals and each of said third metal or metals.
 17. The composition of claim 14 or 15 wherein the conditions of said first calcination step comprise a temperature in the range of 450° to 800° C. and a duration of 1 to 30 hours.
 18. The composition of claim 17 wherein said temperature is in the range of 550° to 750° C.
 19. The composition of claim 14 or 15 wherein the conditions of said second calcination step comprise a temperature in the range of 400° to 700° C. and a duration of 1 to 30 hours.
 20. The composition of claim 19 wherein said temperature is in the range of 450° to 550° C.
 21. The composition of claim 14 or 15 wherein said support comprises oxide or hydroxide of zirconium, titanium, or aluminum or mixtures thereof.
 22. The composition of claim 14 or 15 wherein said support comprises oxide or hydroxide of zirconium.
 23. The composition of claim 14 or 15 wherein said first metal is platinum.
 24. The composition of claim 14 or 15 wherein said second metal is iron.
 25. The composition of claim 14 or 15 wherein said third metal is manganese.
 26. The composition of claim 14 or 15 wherein said first metal is platinum and rhenium, said second metal is iron, and said third metal is manganese.
 27. The composition of claim 14 or 15 wherein said first metal is nickel, said second metal is iron, and said third metal is manganese.
 28. A process for preparing a catalyst which comprises:(a) sulfating a support comprising oxide or hydroxide of Group III or Group IV elements; (b) heating said support in a first calcination step; (c) introducing a first metal on said support, said first metal comprising a metal or mixture of metals selected from the group consisting of platinum; palladium; nickel; platinum and rhenium; and platinum and tin; and combinations thereof; and (d) heating said support anti said first metal in a second calcination step;wherein the conditions of said second calcination step comprise a lower temperature than said first calcination step.
 29. The process of claim 28 wherein the conditions of said first calcination step comprise a temperature in the range of 450° to 800° C. and a duration of 1 to 30 hours.
 30. The process of claim 29 wherein said temperature is in the range of 550° to 750° C.
 31. The process of claim 28 wherein the conditions of said first calcination step comprise a temperature in the range of 400° to 700° C. and a duration of 1 to 30 hours.
 32. The process of claim 31 wherein said temperature is in the range of 450° to 550° C.
 33. The process of claim 28 wherein said process further comprises introducing on said support prior to said first calcination step at least one second metal selected from the group consisting of Group VIII metals.
 34. The process of claim 28 wherein said process further comprises introducing on said support prior to said first calcination step at least one additional metal selected from the group consisting of Group V, Group VI and Group VII metals.
 35. The process of claim 28 wherein said process further comprises introducing on said support prior to said first calcination step at least one second metal selected from the group consisting of Group VIII metals and at least one third metal selected from the group consisting of Group V, Group VI and Group VII metals.
 36. The process of claim 35 wherein said first calcination step comprises separately calcining said sulfated support, said second metal and said third metal subsequent to the introduction of each of said second metal or metals and each of said third metal or metals. 